Fungicidal compositions including hydrazone derivatives and copper

ABSTRACT

The present invention relates to the use of hydrazone compounds and copper for controlling the growth of fungi.

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of U.S. Provisional PatentApplication Ser. No. 61/144,560 filed Jan. 14, 2009, which isincorporated by reference herein.

FIELD OF THE INVENTION

The present disclosure relates to hydrazone compounds, optionally withand without copper, and their use as fungicides. The compounds of thepresent disclosure may offer protection against ascomycetes,basidiomycetes, deuteromycetes and oomycetes.

BACKGROUND

Copper is used to control the growth of organisms, especiallymicroorganisms, in a variety of applications such as those described inthe “Handbook of copper compounds and applications” edited by H. W.Richardson and published by Marcel Dekker, Inc. New York (1997), whichis expressly incorporated by reference herein. These applications mayinclude its use in agriculture to control a wide range of fungal andbacterial diseases of plants. Copper products may also be used asaquatic biocides in fresh or marine environments. Copper products may beused in antifouling applications and to control unwanted organisms inponds and lakes based on the toxicity of copper towards algae, fungi,macrophytes and mollusks. Copper-based materials may also be used aswood preservatives and on other materials to inhibit fungal andbacterial growth. Other uses also include killing plant roots in sewersystems.

Ecological risk assessment studies have shown that copper products,which normally are applied at high use rates, may be toxic to birds,mammals, fish and other aquatic species (“Reregistration EligibilityDecision (RED) for Coppers”, EPA 738-R-06-020, July 2006, which isexpressly incorporated by reference herein). Thus, while copper is ahighly useful agent for controlling the growth of undesirable organismsin different environments, it is desirable to minimize the amount ofcopper applied.

Fungicides are compounds, of natural or synthetic origin, which act toprotect and/or cure plants against damage caused by agriculturallyrelevant fungi. Generally, no single fungicide is useful in allsituations. Consequently, research is ongoing to produce fungicides thatmay have better performance, are easier to use, and cost less.

SUMMARY OF THE INVENTION

One embodiment of the present disclosure may include compounds ofFormula I:

wherein R1 is CH3 or CH2CH3;

Y2 is H, halogen, hydroxyl, nitro, cyano, C1-C4 alkyl, C1-C4 alkoxy,C1-C4 fluoroalkyl, and C1-C4 fluoroalkoxy,

Y3, Y4, Y5, and Y6 are independently selected from the group consistingof halogen, nitro, cyano, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 fluoroalkyl,and C1-C4 fluoroalkoxy;

with the proviso that

Y2, Y3, Y4, Y5, and Y6 are not all H;

if Y3, Y4, Y5, and Y6 are all H, Y2 is not hydroxyl, Cl, or F;

if Y2, Y3, Y5, and Y6 are all H and R1 is CH3, Y4 is not CH3, OCH2CH3,or t-butyl;

if Y2, Y3, Y5, and Y6 are all H, Y4 is not F or Br;

if Y2, Y5, and Y6 are H, Y3 and Y4 are not both OCH3;

if R is CH3 and Y2, Y4, and Y6 are H, Y3 and Y4 are not both OCH3 orNO2; and

if R CH2CH3 and Y2 and Y6 are H, Y3, Y4, and Y5 are not all OCH3.

Another embodiment of the present disclosure may include a fungicidalcomposition for the control or prevention of fungal attack comprisingthe compounds described below and a phytologically acceptable carriermaterial.

Yet another embodiment of the present disclosure may include a methodfor the control or prevention of fungal attack on a plant, the methodincluding the steps of applying a fungicidally effective amount of oneor more of the compounds described below to at least one of the fungus,the plant, an area adjacent to the plant, and the seed adapted toproduce the plant.

The term “alkyl” refers to a branched, unbranched, or cyclic carbonchain, including methyl, ethyl, propyl, butyl, isopropyl, isobutyl,tertiary butyl, pentyl, hexyl, cyclopropyl, cyclobutyl, cyclopentyl,cyclohexyl and the like.

The term “cycloalkyl” refers to a monocyclic or polycyclic, saturatedsubstituent consisting of carbon and hydrogen.

The term “alkenyl” refers to a branched, unbranched or cyclic carbonchain containing one or more double bonds including ethenyl, propenyl,butenyl, isopropenyl, isobutenyl, cyclohexenyl, and the like.

The term “alkynyl” refers to a branched or unbranched carbon chaincontaining one or more triple bonds including propynyl, butynyl and thelike.

As used throughout this specification, the term ‘R’ refers to the groupconsisting of C1-C4 alkyl, C2-C4 alkenyl, C2-C4 alkynyl, C3-C6cycloalkyl, C1-C4 haloalkyl, C2-C4 haloalkenyl, C2-C4 haloalkynyl, orC3-C6 halocycloalkyl, unless stated otherwise.

The term “alkoxy” refers to an —OR substituent.

The term “alkylthio” refers to an —S—R substituent.

The term “haloalkylthio” refers to an alkylthio, which is substitutedwith Cl, F, I, or Br or any combination thereof.

The term “cyano” refers to a —C≡N substituent.

The term “hydroxyl” refers to an —OH substituent.

The term “haloalkoxy” refers to an —OR—X substituent, wherein X is Cl,F, Br, or I, or any combination thereof.

The term “haloalkyl” refers to an alkyl, which is substituted with Cl,F, I, or Br or any combination thereof.

The term “halocycloalkyl” refers to a monocyclic or polycyclic,saturated substituent consisting of carbon and hydrogen, which issubstituted with Cl, F, I, or Br or any combination thereof.

The term “haloalkenyl” refers to an alkenyl, which is substituted withCl, F, I, or Br or any combination thereof.

The term “haloalkynyl” refers to an alkynyl which is substituted withCl, F, I, or Br or any combination thereof.

The term “halogen” or “halo” refers to one or more halogen atoms,defined as F, Cl, Br, and I.

The term “nitro” refers to a —NO₂ substituent.

The term “aryl” refers to a cyclic, aromatic substituent consisting ofhydrogen and carbon.

The term “heteroaryl” refers to a cyclic substituent that may be fullyunsaturated, where the cyclic structure contains at least one carbon andat least one heteroatom, where said heteroatom is nitrogen, sulfur, oroxygen.

Throughout the disclosure, reference to the compounds of Formula I isread as also including optical isomers and salts of Formula I, andhydrates thereof. Specifically, when Formula I contains a branched chainalkyl group, it is understood that such compounds include opticalisomers and racemates thereof. Exemplary salts include: hydrochloride,hydrobromide, hydroiodide, and the like.

Certain compounds disclosed in this document can exist as one or moreisomers. The various isomers include stereoisomers, geometric isomers,diastereomers, and enantiomers. Thus, the compounds disclosed in thisinvention include geometric isomers, racemic mixtures, individualstereoisomers, and optically active mixtures. It will be appreciated bythose skilled in the art that one isomer may be more active than theothers. The structures disclosed in the present disclosure are drawn inonly one geometric form for clarity, but are intended to represent allgeometric forms of the molecule.

It is also understood by those skilled in the art that additionalsubstitution is allowable, unless otherwise noted, as long as the rulesof chemical bonding and strain energy are satisfied and the productstill exhibits fungicidal activity.

Another embodiment of the present disclosure is a use of a compound ofFormula I, for protection of a plant against attack by a phytopathogenicorganism or the treatment of a plant infested by a phytopathogenicorganism, comprising the application of a compound of Formula I, or acomposition comprising the compound to soil, a plant, a part of a plant,foliage, and/or seeds.

Additionally, another embodiment of the present disclosure is acomposition useful for protecting a plant against attack by aphytopathogenic organism and/or treatment of a plant infested by aphytopathogenic organism comprising a compound of Formula I and aphytologically acceptable carrier material.

Additional features and advantages of the present invention will becomeapparent to those skilled in the art upon consideration of the followingdetailed description of the illustrative embodiments exemplifying thebest mode of carrying out the invention as presently perceived.

DETAILED DESCRIPTION OF THE DISCLOSURE

The compounds of the present disclosure may be applied by any of avariety of known techniques, either as the compounds or as formulationscomprising the compounds. For example, the compounds may be applied tothe roots, seeds or foliage of plants for the control of various fungi,without damaging the commercial value of the plants. The materials maybe applied in the form of any of the generally used formulation types,for example, as solutions, dusts, wettable powders, flowableconcentrates, or emulsifiable concentrates.

The embodiments of the invention described herein are not intended to beexhaustive or to limit the invention to the precise forms disclosed.Rather, the embodiments selected for description have been chosen toenable one skilled in the art to practice the invention. Although thedisclosure is described as a synergistic combination of copper,copper-based fungicides, or other copper-containing materials and ahydrazone or hydrazone derivative it should be understood that theconcepts presented herein may be used in various applications and shouldnot be limited.

The compounds of the present invention have fungitoxic activity againstphytopathogenic fungi, against fungal pathogens of mammals, includinghumans, and against wood decay causing fungi. The compounds of thepresent invention may have broad spectrum fungitoxic activity,particularly against phytopathogenic fungi. They are active againstfungi of a number of classes including Deuteromycetes (FungiImperfecti), Basidiomycetes, Oomycetes and Ascomycetes. Moreparticularly, the method of this invention provides for activity againstorganisms including, but not limited to, Phytophthora species,Plasmopara viticola, Pseudoperonospora cubensis, Pythium species,Pyricularia oryzae, Colletotrichum species, Helminthosporium species,Alternaria species, Septoria nodorum, Septoria tritici, Leptosphaerianodorum, Ustilago maydis, Erysiphe graminis, Puccinia species,Sclerotinia species, Sphaerotheca fuliginea, Cercospora species,Rhizoctonia species, Uncinula necator and Podosphaera leucotricha.

The method of the present invention also provides for activity againstfungal pathogens of mammals (including humans) including, but notlimited to, Candida species such as C. albicans, C. glabrata, C.parapsilosis, C. krusei, and C. tropicalis, Aspergillus species such asAspergillus fumigatus, Fusarium species, Coccidioides immitis,Cryptococcus neoformans, Histoplasma capsulatum, Microsporum species,and Tricophyton species. The method of the present invention alsoprovides for activity against fungi which cause wood decay such asGleophyllum trabeur, Phialophora mutabilis, Poria palcenta and Trametesversicolor.

Preferably, the compounds of the present disclosure are applied in theform of a formulation, comprising one or more of the compounds ofFormula I with a phytologically acceptable carrier. Concentratedformulations may be dispersed in water, or other liquids, forapplication, or formulations may be dust-like or granular, which maythen be applied without further treatment. The formulations can beprepared according to procedures that are conventional in theagricultural chemical art.

The present disclosure contemplates all vehicles by which one or more ofthe compounds may be formulated for delivery and use as a fungicide.Typically, formulations are applied as aqueous suspensions or emulsions.Such suspensions or emulsions may be produced from water-soluble, watersuspendible, or emulsifiable formulations which are solids, usuallyknown as wettable powders; or liquids, usually known as emulsifiableconcentrates, aqueous suspensions, or suspension concentrates. As willbe readily appreciated, any material to which these compounds may beadded may be used, provided it yields the desired utility withoutsignificant interference with the activity of these compounds asantifungal agents.

Wettable powders, which may be compacted to form water dispersiblegranules, comprise an intimate mixture of one or more of the compoundsof Formula I, an inert carrier and surfactants. The concentration of thecompound in the wettable powder may be from about 10 percent to about 90percent by weight based on the total weight of the wettable powder, morepreferably about 25 weight percent to about 75 weight percent. In thepreparation of wettable powder formulations, the compounds may becompounded with any finely divided solid, such as prophyllite, talc,chalk, gypsum, Fuller's earth, bentonite, attapulgite, starch, casein,gluten, montmorillonite clays, diatomaceous earths, purified silicatesor the like. In such operations, the finely divided carrier andsurfactants are typically blended with the compound(s) and milled.

Emulsifiable concentrates of the compounds of Formula I may comprise aconvenient concentration, such as from about 10 weight percent to about50 weight percent of the compound, in a suitable liquid, based on thetotal weight of the concentrate. The compounds may be dissolved in aninert carrier, which is either a water-miscible solvent or a mixture ofwater-immiscible organic solvents, and emulsifiers. The concentrates maybe diluted with water and oil to form spray mixtures in the form ofoil-in-water emulsions. Useful organic solvents include aromatics,especially the high-boiling naphthalenic and olefinic portions ofpetroleum such as heavy aromatic naphtha. Other organic solvents mayalso be used, for example, terpenic solvents, including rosinderivatives, aliphatic ketones, such as cyclohexanone, and complexalcohols, such as 2-ethoxyethanool.

Emulsifiers which may be advantageously employed herein may be readilydetermined by those skilled in the art and include various nonionic,anionic, cationic and amphoteric emulsifiers, or a blend of two or moreemulsifiers. Examples of nonionic emulsifiers useful in preparing theemulsifiable concentrates include the polyalkylene glycol ethers andcondensation products of alkyl and aryl phenols, aliphatic alcohols,aliphatic amines or fatty acids with ethylene oxide, propylene oxidessuch as the ethoxylated alkyl phenols and carboxylic esters solubilizedwith the polyol or polyoxyalkylene. Cationic emulsifiers includequaternary ammonium compounds and fatty amine salts. Anionic emulsifiersinclude the oil-soluble salts (e.g., calcium) of alkylaryl sulphonicacids, oil-soluble salts or sulfated polyglycol ethers and appropriatesalts of phosphated polyglycol ether.

Representative organic liquids which may be employed in preparing theemulsifiable concentrates of the compounds of the present invention arethe aromatic liquids such as xylene, propyl benzene fractions; or mixednaphthalene fractions, mineral oils, substituted aromatic organicliquids such as dioctyl phthalate; kerosene; dialkyl amides of variousfatty acids, particularly the dimethyl amides of fatty glycols andglycol derivatives such as the n-butyl ether, ethyl ether or methylether of diethylene glycol, and the methyl ether of triethylene glycoland the like. Mixtures of two or more organic liquids may also beemployed in the preparation of the emulsifiable concentrate. Organicliquids include xylene, and propyl benzene fractions, with xylene beingmost preferred in some cases. Surface-active dispersing agents aretypically employed in liquid formulations and in an amount of from 0.1to 20 percent by weight based on the combined weight of the dispersingagent with one or more of the compounds. The formulations can alsocontain other compatible additives, for example, plant growth regulatorsand other biologically active compounds used in agriculture.

Aqueous suspensions comprise suspensions of one or more water-insolublecompounds of Formula I, dispersed in an aqueous vehicle at aconcentration in the range from about 5 to about 50 weight percent,based on the total weight of the aqueous suspension. Suspensions areprepared by finely grinding one or more of the compounds, and vigorouslymixing the ground material into a vehicle comprised of water andsurfactants chosen from the same types discussed above. Othercomponents, such as inorganic salts and synthetic or natural gums, mayalso be added to increase the density and viscosity of the aqueousvehicle. It is often most effective to grind and mix at the same time bypreparing the aqueous mixture and homogenizing it in an implement suchas a sand mill, ball mill, or piston-type homogenizer.

Aqueous emulsions comprise emulsions of one or more water-insolublepesticidally active ingredients emulsified in an aqueous vehicle at aconcentration typically in the range from about 5 to about 50 weightpercent, based on the total weight of the aqueous emulsion. If thepesticidally active ingredient is a solid it must be dissolved in asuitable water-immiscible solvent prior to the preparation of theaqueous emulsion. Emulsions are prepared by emulsifying the liquidpesticidally active ingredient or water-immiscible solution thereof intoan aqueous medium typically with inclusion of surfactants that aid inthe formation and stabilization of the emulsion as described above. Thisis often accomplished with the aid of vigorous mixing provided by highshear mixers or homogenizers.

The compounds of Formula I can also be applied as granular formulations,which are particularly useful for applications to the soil. Granularformulations generally contain from about 0.5 to about 10 weightpercent, based on the total weight of the granular formulation of thecompound(s), dispersed in an inert carrier which consists entirely or inlarge part of coarsely divided inert material such as attapulgite,bentonite, diatomite, clay or a similar inexpensive substance. Suchformulations are usually prepared by dissolving the compounds in asuitable solvent and applying it to a granular carrier which has beenpreformed to the appropriate particle size, in the range of from about0.5 to about 3 mm. A suitable solvent is a solvent in which the compoundis substantially or completely soluble. Such formulations may also beprepared by making a dough or paste of the carrier and the compound andsolvent, and crushing and drying to obtain the desired granularparticle.

Dusts containing the compounds of Formula I may be prepared byintimately mixing one or more of the compounds in powdered form with asuitable dusty agricultural carrier, such as, for example, kaolin clay,ground volcanic rock, and the like. Dusts can suitably contain fromabout 1 to about 10 weight percent of the compounds, based on the totalweight of the dust.

The formulations may additionally contain adjuvant surfactants toenhance deposition, wetting and penetration of the compounds onto thetarget crop and organism. These adjuvant surfactants may optionally beemployed as a component of the formulation or as a tank mix. The amountof adjuvant surfactant will typically vary from 0.01 to 1.0 percent byvolume, based on a spray-volume of water, preferably 0.05 to 0.5 volumepercent.

Suitable adjuvant surfactants include, but are not limited toethoxylated nonyl phenols, ethoxylated synthetic or natural alcohols,salts of the esters or sulphosuccinic acids, ethoxylatedorganosilicones, ethoxylated fatty amines and blends of surfactants withmineral or vegetable oils. The formulations may also includeoil-in-water emulsions such as those disclosed in U.S. patentapplication Ser. No. 11/495,228, the disclosure of which is expresslyincorporated by reference herein.

The formulations may optionally include combinations that contain otherpesticidal compounds. Such additional pesticidal compounds may befungicides, insecticides, herbicides, nematocides, miticides,arthropodicides, bactericides or combinations thereof that arecompatible with the compounds of the present invention in the mediumselected for application, and not antagonistic to the activity of thepresent compounds. Accordingly, in such embodiments, the otherpesticidal compound is employed as a supplemental toxicant for the sameor for a different pesticidal use. The compounds of Formula I and thepesticidal compound in the combination can generally be present in aweight ratio of from 1:100 to 100:1.

For pharmaceutical use, the compounds described herein may be taken upin pharmaceutically acceptable carriers, such as, for example,solutions, suspensions, tablets, capsules, ointments, elixirs andinjectable compositions. Pharmaceutical preparations may contain from0.1% to 99% by weight of active ingredient. Preparations which are insingle dose form, “unit dosage form”, preferably contain from 20% to 90%active ingredient, and preparations which are not in single dose formpreferably contain from 5% to 20% active ingredient. As used herein, theterm “active ingredient” refers to compounds described herein, saltsthereof, and mixtures of compounds described herein with otherpharmaceutically active compounds. Dosage unit forms such as, forexample, tablets or capsules, typically contain from about 0.05 to about1.0 g of active ingredient.

Suitable means of administering the pharmaceutical preparations includeoral, rectal, topical (including dermal, buccal and sublingual),vaginal, parenteral (including subcutaneous, intramuscular, intravenous,intradermal, intrathecal and epidural) and by naso-gastric tube. It willbe understood by those skilled in the art that the preferred route ofadministration will depend upon the condition being treated and may varywith factors such as the condition of the recipient.

The compounds of the present disclosure may also be combined with otherfungicides to form fungicidal mixtures and synergistic mixtures thereof.The fungicidal compounds of the present disclosure are often applied inconjunction with one or more other fungicides to control a wider varietyof undesirable diseases. When used in conjunction with otherfungicide(s), the presently claimed compounds may be formulated with theother fungicide(s), tank mixed with the other fungicide(s) or appliedsequentially with the other fungicide(s). Such other fungicides mayinclude 2-(thiocyanatomethylthio)-benzothiazole, 2-phenylphenol,8-hydroxyquinoline sulfate, ametoctradin, amisulbrom, antimycin,Ampelomyces quisqualis, azaconazole, azoxystrobin, Bacillus subtilis,benalaxyl, benomyl, benthiavalicarb-isopropyl,benzylaminobenzene-sulfonate (BABS) salt, bicarbonates, biphenyl,bismerthiazol, bitertanol, bixafen, blasticidin-S, borax, Bordeauxmixture, boscalid, bromuconazole, bupirimate, calcium polysulfide,captafol, captan, carbendazim, carboxin, carpropamid, carvone,chloroneb, chlorothalonil, chlozolinate, Coniothyrium minitans, copperhydroxide, copper octanoate, copper oxychloride, copper sulfate, coppersulfate (tribasic), cuprous oxide, cyazofamid, cyflufenamid, cymoxanil,cyproconazole, cyprodinil, dazomet, debacarb, diammoniumethylenebis-(dithiocarbamate), dichlofluanid, dichlorophen, diclocymet,diclomezine, dichloran, diethofencarb, difenoconazole, difenzoquat ion,diflumetorim, dimethomorph, dimoxystrobin, diniconazole, diniconazole-M,dinobuton, dinocap, diphenylamine, dithianon, dodemorph, dodemorphacetate, dodine, dodine free base, edifenphos, enestrobin,epoxiconazole, ethaboxam, ethoxyquin, etridiazole, famoxadone,fenamidone, fenarimol, fenbuconazole, fenfuram, fenhexamid, fenoxanil,fenpiclonil, fenpropidin, fenpropimorph, fentin, fentin acetate, fentinhydroxide, ferbam, ferimzone, fluazinam, fludioxonil, flumorph,fluopicolide, fluopyram, fluoroimide, fluoxastrobin, fluquinconazole,flusilazole, flusulfamide, flutianil, flutolanil, flutriafol,fluxapyroxad, folpet, formaldehyde, fosetyl, fosetyl-aluminium,fuberidazole, furalaxyl, furametpyr, guazatine, guazatine acetates,GY-81, hexachlorobenzene, hexaconazole, hymexazol, imazalil, imazalilsulfate, imibenconazole, iminoctadine, iminoctadine triacetate,iminoctadine tris(albesilate), ipconazole, iprobenfos, iprodione,iprovalicarb, isoprothiolane, isopyrazam, isotianil, kasugamycin,kasugamycin hydrochloride hydrate, kresoxim-methyl, mancopper, mancozeb,mandipropamid, maneb, mepanipyrim, mepronil, mercuric chloride, mercuricoxide, mercurous chloride, metalaxyl, mefenoxam, metalaxyl-M, metam,metam-ammonium, metam-potassium, metam-sodium, metconazole,methasulfocarb, methyl iodide, methyl isothiocyanate, metiram,metominostrobin, metrafenone, mildiomycin, myclobutanil, nabam,nitrothal-isopropyl, nuarimol, octhilinone, ofurace, oleic acid (fattyacids), orysastrobin, oxadixyl, oxine-copper, oxpoconazole fumarate,oxycarboxin, pefurazoate, penconazole, pencycuron, penflufen,pentachlorophenol, pentachlorophenyl laurate, penthiopyrad,phenylmercury acetate, phosphonic acid, phthalide, picoxystrobin,polyoxin B, polyoxins, polyoxorim, potassium bicarbonate, potassiumhydroxyquinoline sulfate, probenazole, prochloraz, procymidone,propamocarb, propamocarb hydrochloride, propiconazole, propineb,proquinazid, prothioconazole, pyraclostrobin, pyrametostrobin,pyraoxystrobin, pyrazophos, pyribencarb, pyributicarb, pyrifenox,pyrimethanil, pyroquilon, quinoclamine, quinoxyfen, quintozene,Reynoutria sachalinensis extract, sedaxane, silthiofam, simeconazole,sodium 2-phenylphenoxide, sodium bicarbonate, sodiumpentachlorophenoxide, spiroxamine, sulfur, SYP-Z071, SYP-Z048, tar oils,tebuconazole, tebufloquin, tecnazene, tetraconazole, thiabendazole,thifluzamide, thiophanate-methyl, thiram, tiadinil, tolclofos-methyl,tolylfluanid, triadimefon, triadimenol, triazoxide, tricyclazole,tridemorph, trifloxystrobin, triflumizole, triforine, triticonazole,validamycin, valifenalate, valiphenal, vinclozolin, zineb, ziram,zoxamide, Candida oleophila, Fusarium oxysporum, Gliocladium spp.,Phlebiopsis gigantea, Streptomyces griseoviridis, Trichoderma spp.,(RS)-N-(3,5-dichlorophenyl)-2-(methoxymethyl)-succinimide,1,2-dichloropropane, 1,3-dichloro-1,1,3,3-tetrafluoroacetone hydrate,1-chloro-2,4-dinitronaphthalene, 1-chloro-2-nitropropane,2-(2-heptadecyl-2-imidazolin-1-yl)ethanol,2,3-dihydro-5-phenyl-1,4-dithi-ine 1,1,4,4-tetraoxide,2-methoxyethylmercury acetate, 2-methoxyethylmercury chloride,2-methoxyethylmercury silicate, 3-(4-chlorophenyl)-5-methylrhodanine,4-(2-nitroprop-1-enyl)phenyl thiocyanateme, ampropylfos, anilazine,azithiram, barium polysulfide, Bayer 32394, benodanil, benquinox,bentaluron, benzamacril; benzamacril-isobutyl, benzamorf, binapacryl,bis(methylmercury) sulfate, bis(tributyltin) oxide, buthiobate, cadmiumcalcium copper zinc chromate sulfate, carbamorph, CECA, chlobenthiazone,chloraniformethan, chlorfenazole, chlorquinox, climbazole, cyclafuramid,cypendazole, cyprofuram, decafentin, dichlone, dichlozoline,diclobutrazol, dimethirimol, dinocton, dinosulfon, dinoterbon,dipyrithione, ditalimfos, dodicin, drazoxolon, EBP, ESBP, etaconazole,etem, ethirim, fenaminosulf, fenapanil, fenitropan, 5-fluorocytosine andprofungicides thereof, fluotrimazole, furcarbanil, furconazole,furconazole-cis, furmecyclox, furophanate, glyodine, griseofulvin,halacrinate, Hercules 3944, hexylthiofos, ICIA0858, isopamphos,isovaledione, mebenil, mecarbinzid, metazoxolon, methfuroxam,methylmercury dicyandiamide, metsulfovax, milneb, mucochloric anhydride,myclozolin, N-3,5-dichlorophenyl-succinimide,N-3-nitrophenylitaconimide, natamycin,N-ethylmercurio-4-toluenesulfonanilide, nickelbis(dimethyldithiocarbamate), OCH, phenylmercurydimethyldithiocarbamate, phenylmercury nitrate, phosdiphen, picolinamideUK-2A and derivatives thereof, prothiocarb; prothiocarb hydrochloride,pyracarbolid, pyridinitril, pyroxychlor, pyroxyfur, quinacetol;quinacetol sulfate, quinazamid, quinconazole, rabenzazole,salicylanilide, SSF-109, sultropen, tecoram, thiadifluor, thicyofen,thiochlorfenphim, thiophanate, thioquinox, tioxymid, triamiphos,triarimol, triazbutil, trichlamide, urbacid, XRD-563, and zarilamide,IK-1140, and any combinations thereof.

The compounds of the present invention can also be combined with otherantifungal compounds used to control infections in mammals to formfungicidal mixtures and synergistic mixtures thereof. The fungicidalcompounds of the present invention can be applied in conjunction withone or more other antifungal compounds or their pharmaceuticallyacceptable salts to control a wider variety of undesirable diseases.When used in conjunction with other antifungal compounds, the presentlyclaimed compounds can be formulated with the other antifungalcompound(s), coadministered with the other antifungal compound(s) orapplied sequentially with the other antifungal compound(s). Typicalantifungal compounds include, but are not limited to compounds selectedfrom the group consisting of an azole such as fluconazole, voriconazole,itraconazole, ketoconazole, and miconazole, a polyene such asamphotericin B, nystatin or liposomal and lipid forms thereof such asAbelcet, AmBisome and Amphocil, a purine nucleotide inhibitor such as5-fluorocytosine, a polyoxin such as nikkomycin, and pneumocandin orechinocandin derivatives such as caspofungin and micofungin.

Additionally, the compounds of the present invention may be combinedwith other pesticides, including insecticides, nematocides, miticides,arthropodicides, bactericides or combinations thereof that arecompatible with the compounds of the present invention in the mediumselected for application, and not antagonistic to the activity of thepresent compounds to form pesticidal mixtures and synergistic mixturesthereof. The fungicidal compounds of the present disclosure may beapplied in conjunction with one or more other pesticides to control awider variety of undesirable pests. When used in conjunction with otherpesticides, the presently claimed compounds may be formulated with theother pesticide(s), tank mixed with the other pesticide(s) or appliedsequentially with the other pesticide(s). Typical insecticides include,but are not limited to: antibiotic insecticides such as allosamidin andthuringiensin; macrocyclic lactone insecticides such as spinosad andspinetoram; avermectin insecticides such as abamectin, doramectin,emamectin, eprinomectin, ivermectin and selamectin; milbemycininsecticides such as lepimectin, milbemectin, milbemycin oxime andmoxidectin; arsenical insecticides such as calcium arsenate, copperacetoarsenite, copper arsenate, lead arsenate, potassium arsenite andsodium arsenite; botanical insecticides such as anabasine, azadirachtin,d-limonene, nicotine, pyrethrins, cinerins, cinerin I, cinerin II,jasmolin I, jasmolin II, pyrethrin I, pyrethrin II, quassia, rotenone,ryania and sabadilla; carbamate insecticides such as bendiocarb andcarbaryl; benzofuranyl methylcarbamate insecticides such as benfuracarb,carbofuran, carbosulfan, decarbofuran and furathiocarb;dimethylcarbamate insecticides dimitan, dimetilan, hyquincarb andpirimicarb; oxime carbamate insecticides such as alanycarb, aldicarb,aldoxycarb, butocarboxim, butoxycarboxim, methomyl, nitrilacarb, oxamyl,tazimcarb, thiocarboxime, thiodicarb and thiofanox; phenylmethylcarbamate insecticides such as allyxycarb, aminocarb, bufencarb,butacarb, carbanolate, cloethocarb, dicresyl, dioxacarb, EMPC,ethiofencarb, fenethacarb, fenobucarb, isoprocarb, methiocarb,metolcarb, mexacarbate, promacyl, promecarb, propoxur, trimethacarb, XMCand xylylcarb; dessicant insecticides such as boric acid, diatomaceousearth and silica gel; diamide insecticides such as chlorantraniliprole,cyantraniliprole and flubendiamide; dinitrophenol insecticides such asdinex, dinoprop, dinosam and DNOC; fluorine insecticides such as bariumhexafluorosilicate, cryolite, sodium fluoride, sodium hexafluorosilicateand sulfluramid; formamidine insecticides such as amitraz,chlordimeform, formetanate and formparanate; fumigant insecticides suchas acrylonitrile, carbon disulfide, carbon tetrachloride, chloroform,chloropicrin, para-dichlorobenzene, 1,2-dichloropropane, ethyl formate,ethylene dibromide, ethylene dichloride, ethylene oxide, hydrogencyanide, iodomethane, methyl bromide, methylchloroform, methylenechloride, naphthalene, phosphine, sulfuryl fluoride andtetrachloroethane; inorganic insecticides such as borax, calciumpolysulfide, copper oleate, mercurous chloride, potassium thiocyanateand sodium thiocyanate; chitin synthesis inhibitors such asbistrifluoron, buprofezin, chlorfluazuron, cyromazine, diflubenzuron,flucycloxuron, flufenoxuron, hexaflumuron, lufenuron, novaluron,noviflumuron, penfluoron, teflubenzuron and triflumuron; juvenilehormone mimics such as epofenonane, fenoxycarb, hydroprene, kinoprene,methoprene, pyriproxyfen and triprene; juvenile hormones such asjuvenile hormone I, juvenile hormone II and juvenile hormone III;moulting hormone agonists such as chromafenozide, halofenozide,methoxyfenozide and tebufenozide; moulting hormones such as α-ecdysoneand ecdysterone; moulting inhibitors such as diofenolan; precocenes suchas precocene I, precocene II and precocene III; unclassified insectgrowth regulators such as dicyclanil; nereistoxin analogue insecticidessuch as bensultap, cartap, thiocyclam and thiosultap; nicotinoidinsecticides such as flonicamid; nitroguanidine insecticides such asclothianidin, dinotefuran, imidacloprid and thiamethoxam; nitromethyleneinsecticides such as nitenpyram and nithiazine; pyridylmethyl-amineinsecticides such as acetamiprid, imidacloprid, nitenpyram andthiacloprid; organochlorine insecticides such as bromo-DDT, camphechlor,DDT, pp′-DDT, ethyl-DDD, HCH, gamma-HCH, lindane, methoxychlor,pentachlorophenol and TDE; cyclodiene insecticides such as aldrin,bromocyclen, chlorbicyclen, chlordane, chlordecone, dieldrin, dilor,endosulfan, alpha-endosulfan, endrin, HEOD, heptachlor, HHDN, isobenzan,isodrin, kelevan and mirex; organophosphate insecticides such asbromfenvinfos, chlorfenvinphos, crotoxyphos, dichlorvos, dicrotophos,dimethylvinphos, fospirate, heptenophos, methocrotophos, mevinphos,monocrotophos, naled, naftalofos, phosphamidon, propaphos, TEPP andtetrachlorvinphos; organothiophosphate insecticides such asdioxabenzofos, fosmethilan and phenthoate; aliphatic organothiophosphateinsecticides such as acethion, amiton, cadusafos, chlorethoxyfos,chlormephos, demephion, demephion-O, demephion-S, demeton, demeton-O,demeton-S, demeton-methyl, demeton-O-methyl, demeton-S-methyl,demeton-S-methylsulphon, disulfoton, ethion, ethoprophos, IPSP,isothioate, malathion, methacrifos, oxydemeton-methyl, oxydeprofos,oxydisulfoton, phorate, sulfotep, terbufos and thiometon; aliphaticamide organothiophosphate insecticides such as amidithion, cyanthoate,dimethoate, ethoate-methyl, formothion, mecarbam, omethoate, prothoate,sophamide and vamidothion; oxime organothiophosphate insecticides suchas chlorphoxim, phoxim and phoxim-methyl; heterocyclicorganothiophosphate insecticides such as azamethiphos, coumaphos,coumithoate, dioxathion, endothion, menazon, morphothion, phosalone,pyraclofos, pyridaphenthion and quinothion; benzothiopyranorganothiophosphate insecticides such as dithicrofos and thicrofos;benzotriazine organothiophosphate insecticides such as azinphos-ethyland azinphos-methyl; isoindole organothiophosphate insecticides such asdialifos and phosmet; isoxazole organothiophosphate insecticides such asisoxathion and zolaprofos; pyrazolopyrimidine organothiophosphateinsecticides such as chlorprazophos and pyrazophos; pyridineorganothiophosphate insecticides such as chlorpyrifos andchlorpyrifos-methyl; pyrimidine organothiophosphate insecticides such asbutathiofos, diazinon, etrimfos, lirimfos, pirimiphos-ethyl,pirimiphos-methyl, primidophos, pyrimitate and tebupirimfos; quinoxalineorganothiophosphate insecticides such as quinalphos andquinalphos-methyl; thiadiazole organothiophosphate insecticides such asathidathion, lythidathion, methidathion and prothidathion; triazoleorganothiophosphate insecticides such as isazofos and triazophos; phenylorganothiophosphate insecticides such as azothoate, bromophos,bromophos-ethyl, carbophenothion, chlorthiophos, cyanophos, cythioate,dicapthon, dichlofenthion, etaphos, famphur, fenchlorphos, fenitrothionfensulfothion, fenthion, fenthion-ethyl, heterophos, jodfenphos,mesulfenfos, parathion, parathion-methyl, phenkapton, phosnichlor,profenofos, prothiofos, sulprofos, temephos, trichlormetaphos-3 andtrifenofos; phosphonate insecticides such as butonate and trichlorfon;phosphonothioate insecticides such as mecarphon; phenylethylphosphonothioate insecticides such as fonofos and trichloronat;phenyl phenylphosphonothioate insecticides such as cyanofenphos, EPN andleptophos; phosphoramidate insecticides such as crufomate, fenamiphos,fosthietan, mephosfolan, phosfolan and pirimetaphos;phosphoramidothioate insecticides such as acephate, isocarbophos,isofenphos, isofenphos-methyl, methamidophos and propetamphos;phosphorodiamide insecticides such as dimefox, mazidox, mipafox andschradan; oxadiazine insecticides such as indoxacarb; oxadiazolineinsecticides such as metoxadiazone; phthalimide insecticides such asdialifos, phosmet and tetramethrin; pyrazole insecticides such astebufenpyrad, tolefenpyrad; phenylpyrazole insecticides such asacetoprole, ethiprole, fipronil, pyrafluprole, pyriprole andvaniliprole; pyrethroid ester insecticides such as acrinathrin,allethrin, bioallethrin, barthrin, bifenthrin, bioethanomethrin,cyclethrin, cycloprothrin, cyfluthrin, beta-cyfluthrin, cyhalothrin,gamma-cyhalothrin, lambda-cyhalothrin, cypermethrin, alpha-cypermethrin,beta-cypermethrin, theta-cypermethrin, zeta-cypermethrin, cyphenothrin,deltamethrin, dimefluthrin, dimethrin, empenthrin, fenfluthrin,fenpirithrin, fenpropathrin, fenvalerate, esfenvalerate, flucythrinate,fluvalinate, tau-fluvalinate, furethrin, imiprothrin, meperfluthrin,metofluthrin, permethrin, biopermethrin, transpermethrin, phenothrin,prallethrin, profluthrin, pyresmethrin, resmethrin, bioresmethrin,cismethrin, tefluthrin, terallethrin, tetramethrin, tetramethylfluthrin,tralomethrin and transfluthrin; pyrethroid ether insecticides such asetofenprox, flufenprox, halfenprox, protrifenbute and silafluofen;pyrimidinamine insecticides such as flufenerim and pyrimidifen; pyrroleinsecticides such as chlorfenapyr; tetramic acid insecticides such asspirotetramat; tetronic acid insecticides such as spiromesifen; thioureainsecticides such as diafenthiuron; urea insecticides such as flucofuronand sulcofuron; and unclassified insecticides such as closantel, coppernaphthenate, crotamiton, EXD, fenazaflor, fenoxacrim, hydramethylnon,isoprothiolane, malonoben, metaflumizone, nifluridide, plifenate,pyridaben, pyridalyl, pyrifluquinazon, rafoxanide, sulfoxaflor,triarathene and triazamate, and any combinations thereof.

Additionally, the compounds of the present invention may be combinedwith herbicides that are compatible with the compounds of the presentinvention in the medium selected for application, and not antagonisticto the activity of the present compounds to form pesticidal mixtures andsynergistic mixtures thereof. The fungicidal compounds of the presentdisclosure may be applied in conjunction with one or more herbicides tocontrol a wide variety of undesirable plants. When used in conjunctionwith herbicides, the presently claimed compounds may be formulated withthe herbicide(s), tank mixed with the herbicide(s) or appliedsequentially with the herbicide(s). Typical herbicides include, but arenot limited to: amide herbicides such as allidochlor, beflubutamid,benzadox, benzipram, bromobutide, cafenstrole, CDEA, cyprazole,dimethenamid, dimethenamid-P, diphenamid, epronaz, etnipromid,fentrazamide, flupoxam, fomesafen, halosafen, isocarbamid, isoxaben,napropamide, naptalam, pethoxamid, propyzamide, quinonamid and tebutam;anilide herbicides such as chloranocryl, cisanilide, clomeprop,cypromid, diflufenican, etobenzanid, fenasulam, flufenacet, flufenican,mefenacet, mefluidide, metamifop, monalide, naproanilide, pentanochlor,picolinafen and propanil; arylalanine herbicides such as benzoylprop,flampropand flamprop-M; chloroacetanilide herbicides such as acetochlor,alachlor, butachlor, butenachlor, delachlor, diethatyl, dimethachlor,metazachlor, metolachlor, S-metolachlor, pretilachlor, propachlor,propisochlor, prynachlor, terbuchlor, thenylchlor and xylachlor;sulfonanilide herbicides such as benzofluor, perfluidone, pyrimisulfanand profluazol; sulfonamide herbicides such as asulam, carbasulam,fenasulam and oryzalin; thioamide herbicides such as chlorthiamid;antibiotic herbicides such as bilanafos; benzoic acid herbicides such aschloramben, dicamba, 2,3,6-TBA and tricamba; pyrimidinyloxybenzoic acidherbicides such as bispyribac and pyriminobac; pyrimidinylthiobenzoicacid herbicides such as pyrithiobac; phthalic acid herbicides such aschlorthal; picolinic acid herbicides such as aminopyralid, clopyralidand picloram; quinolinecarboxylic acid herbicides such as quinclorac andquinmerac; arsenical herbicides such as cacodylic acid, CMA, DSMA,hexaflurate, MAA, MAMA, MSMA, potassium arsenite and sodium arsenite;benzoylcyclohexanedione herbicides such as mesotrione, sulcotrione,tefuryltrione and tembotrione; benzofuranyl alkylsulfonate herbicidessuch as benfuresate and ethofumesate; benzothiazole herbicides such asbenzazolin; carbamate herbicides such as asulam, carboxazolechlorprocarb, dichlormate, fenasulam, karbutilate and terbucarb;carbanilate herbicides such as barban, BCPC, carbasulam, carbetamide,CEPC, chlorbufam, chlorpropham, CPPC, desmedipham, phenisopham,phenmedipham, phenmedipham-ethyl, propham and swep; cyclohexene oximeherbicides such as alloxydim, butroxydim, clethodim, cloproxydim,cycloxydim, profoxydim, sethoxydim, tepraloxydim and tralkoxydim;cyclopropylisoxazole herbicides such as isoxachlortole and isoxaflutole;dicarboximide herbicides such as cinidon-ethyl, flumezin, flumiclorac,flumioxazin and flumipropyn; dinitroaniline herbicides such asbenfluralin, butralin, dinitramine, ethalfluralin, fluchloralin,isopropalin, methalpropalin, nitralin, oryzalin, pendimethalin,prodiamine, profluralin and trifluralin; dinitrophenol herbicides suchas dinofenate, dinoprop, dinosam, dinoseb, dinoterb, DNOC, etinofen andmedinoterb; diphenyl ether herbicides such as ethoxyfen; nitrophenylether herbicides such as acifluorfen, aclonifen, bifenox,chlomethoxyfen, chlornitrofen, etnipromid, fluorodifen, fluoroglycofen,fluoronitrofen, fomesafen, furyloxyfen, halosafen, lactofen, nitrofen,nitrofluorfen and oxyfluorfen; dithiocarbamate herbicides such asdazomet and metam; halogenated aliphatic herbicides such as alorac,chloropon, dalapon, flupropanate, hexachloroacetone, iodomethane, methylbromide, monochloroacetic acid, SMA and TCA; imidazolinone herbicidessuch as imazamethabenz, imazamox, imazapic, imazapyr, imazaquin andimazethapyr; inorganic herbicides such as ammonium sulfamate, borax,calcium chlorate, copper sulfate, ferrous sulfate, potassium azide,potassium cyanate, sodium azide, sodium chlorate and sulfuric acid;nitrile herbicides such as bromobonil, bromoxynil, chloroxynil,dichlobenil, iodobonil, ioxynil and pyraclonil; organophosphorusherbicides such as amiprofos-methyl, anilofos, bensulide, bilanafos,butamifos, 2,4-DEP, DMPA, EBEP, fosamine, glufosinate, glufosinate-P,glyphosate and piperophos; phenoxy herbicides such as bromofenoxim,clomeprop, 2,4-DEB, 2,4-DEP, difenopenten, disul, erbon, etnipromid,fenteracol and trifopsime; oxadiazoline herbicides such as methazole,oxadiargyl, oxadiazon; oxazole herbicides such as fenoxasulfone;phenoxyacetic herbicides such as 4-CPA, 2,4-D, 3,4-DA, MCPA,MCPA-thioethyl and 2,4,5-T; phenoxybutyric herbicides such as 4-CPB,2,4-DB, 3,4-DB, MCPB and 2,4,5-TB; phenoxypropionic herbicides such ascloprop, 4-CPP, dichlorprop, dichlorprop-P, 3,4-DP, fenoprop,mecopropand mecoprop-P; aryloxyphenoxypropionic herbicides such aschlorazifop, clodinafop, clofop, cyhalofop, diclofop, fenoxaprop,fenoxaprop-P, fenthiaprop, fluazifop, fluazifop-P, haloxyfop,haloxyfop-P, isoxapyrifop, metamifop, propaquizafop, quizalofop,quizalofop-P and trifop; phenylenediamine herbicides such as dinitramineand prodiamine; pyrazole herbicides such as pyroxasulfone;benzoylpyrazole herbicides such as benzofenap, pyrasulfotole,pyrazolynate, pyrazoxyfen, and topramezone; phenylpyrazole herbicidessuch as fluazolate, nipyraclofen, pioxaden and pyraflufen; pyridazineherbicides such as credazine, pyridafol and pyridate; pyridazinoneherbicides such as brompyrazon, chloridazon, dimidazon, flufenpyr,metflurazon, norflurazon, oxapyrazon and pydanon; pyridine herbicidessuch as aminopyralid, cliodinate, clopyralid, dithiopyr, fluoroxypyr,haloxydine, picloram, picolinafen, pyriclor, thiazopyr and triclopyr;pyrimidinediamine herbicides such as iprymidam and tioclorim; quaternaryammonium herbicides such as cyperquat, diethamquat, difenzoquat, diquat,morfamquat and paraquat; thiocarbamate herbicides such as butylate,cycloate, di-allate, EPTC, esprocarb, ethiolate, isopolinate,methiobencarb, molinate, orbencarb, pebulate, pro sulfocarb,pyributicarb, sulfallate, thiobencarb, tiocarbazil, tri-allate andvernolate; thiocarbonate herbicides such as dimexano, EXD and proxan;thiourea herbicides such as methiuron; triazine herbicides such asdipropetryn, indaziflam, triaziflam and trihydroxytriazine;chlorotriazine herbicides such as atrazine, chlorazine, cyanazine,cyprazine, eglinazine, ipazine, mesoprazine, procyazine, proglinazine,propazine, sebuthylazine, simazine, terbuthylazine and trietazine;methoxytriazine herbicides such as atraton, methometon, prometon,secbumeton, simeton and terbumeton; methylthiotriazine herbicides suchas ametryn, aziprotryne, cyanatryn, desmetryn, dimethametryn,methoprotryne, prometryn, simetryn and terbutryn; triazinone herbicidessuch as ametridione, amibuzin, hexazinone, isomethiozin, metamitron andmetribuzin; triazole herbicides such as amitrole, cafenstrole, epronazand flupoxam; triazolone herbicides such as amicarbazone, bencarbazone,carfentrazone, flucarbazone, ipfencarbazone, propoxycarbazone,sulfentrazone and thiencarbazone-methyl; triazolopyrimidine herbicidessuch as cloransulam, diclosulam, florasulam, flumetsulam, metosulam,penoxsulam and pyroxsulam; uracil herbicides such as benzfendizone,bromacil, butafenacil, flupropacil, isocil, lenacil, saflufenacil andterbacil; urea herbicides such as benzthiazuron, cumyluron, cycluron,dichloralurea, diflufenzopyr, isonoruron, isouron, methabenzthiazuron,monisouron and noruron; phenylurea herbicides such as anisuron, buturon,chlorbromuron, chloreturon, chlorotoluron, chloroxuron, daimuron,difenoxuron, dimefuron, diuron, fenuron, fluometuron, fluothiuron,isoproturon, linuron, methiuron, methyldymron, metobenzuron,metobromuron, metoxuron, monolinuron, monuron, neburon, parafluoron,phenobenzuron, siduron, tetrafluoron and thidiazuron;pyrimidinylsulfonylurea herbicides such as amidosulfuron, azimsulfuron,bensulfuron, chlorimuron, cyclosulfamuron, ethoxysulfuron,flazasulfuron, flucetosulfuron, flupyrsulfuron, foramsulfuron,halosulfuron, imazosulfuron, mesosulfuron, metazosulfuron, nicosulfuron,orthosulfamuron, oxasulfuron, primisulfuron, propyrisulfuron,pyrazosulfuron, rimsulfuron, sulfometuron, sulfosulfuron andtrifloxysulfuron; triazinylsulfonylurea herbicides such aschlorsulfuron, cinosulfuron, ethametsulfuron, iodosulfuron, metsulfuron,prosulfuron, thifensulfuron, triasulfuron, tribenuron, triflusulfuronand tritosulfuron; thiadiazolylurea herbicides such as buthiuron,ethidimuron, tebuthiuron, thiazafluoron and thidiazuron; andunclassified herbicides such as acrolein, allyl alcohol,aminocyclopyrachlor, azafenidin, bentazone, benzobicyclon,bicyclopyrone, buthidazole, calcium cyanamide, cambendichlor,chlorfenac, chlorfenprop, chlorflurazole, chlorflurenol, cinmethylin,clomazone, CPMF, cresol, cyanamide, ortho-dichlorobenzene, dimepiperate,endothal, fluoromidine, fluridone, fluorochloridone, flurtamone,fluthiacet, indanofan, methyl isothiocyanate, OCH, oxaziclomefone,pentachlorophenol, pentoxazone, phenylmercury acetate, prosulfalin,pyribenzoxim, pyriftalid, quinoclamine, rhodethanil, sulglycapin,thidiazimin, tridiphane, trimeturon, tripropindan and tritac.

The compounds have broad ranges of efficacy as fungicides. The exactamount of the hydrazones and copper-containing materials to be appliedis dependent not only on the specific active materials being applied andrelative amounts of hydrazone and copper in the mixtures, but also onthe particular action desired, the fungal species to be controlled, andthe stage of growth thereof, as well as the part of the plant or otherproduct to be contacted with the compound. Thus, all the compounds, andformulations containing the same, may not be equally effective atsimilar concentrations or against the same fungal species.

Another embodiment of the present disclosure is a method for the controlor prevention of fungal attack. This method comprises applying to thesoil, plant, roots, foliage, seed or locus of the fungus, or to a locusin which the infestation is to be prevented (for example applying tocereal or grape plants), a fungicidally effective amount of one or moreof the compounds of Formula I. The compounds are suitable for treatmentof various plants at fungicidal levels, while exhibiting lowphytotoxicity. The compounds may be useful both in a protectant and/oran eradicant fashion.

The compounds have been found to have significant fungicidal effectparticularly for agricultural use. Many of the compounds areparticularly effective for use with agricultural crops and horticulturalplants.

It will be understood by those in the art that the efficacy of thecompound for the foregoing fungi establishes the general utility of thecompounds as fungicides.

The compounds are effective in use with plants in a disease-inhibitingand phytologically acceptable amount. The term “disease-inhibiting andphytologically acceptable amount” refers to an amount of a compound thatkills or inhibits the plant disease for which control is desired, but isnot significantly toxic to the plant. This amount will generally be fromabout 0.1 to about 1000 ppm (parts per million), with 1 to 500 ppm beingpreferred. The exact amount of a compound required varies with thefungal disease to be controlled, the type of formulation employed, themethod of application, the particular plant species, climate conditions,and the like. A suitable application rate is typically in the range fromabout 0.10 to about 4 pounds/acre (about 0.01 to 0.45 grams per squaremeter, g/m²).

For foliar control of fungal infections on plants, the amount of copperused in mixture with hydrazone may range from 0.001 to 5 kg/ha, andpreferably from 0.05 to 1 kg/ha. The amount of hydrazone used in mixturewith copper may range from 0.001 to 5 kg/ha, and preferably from 0.05 to1 kg/ha. The molar ratio of copper to hydrazone may range from 0.1:1 to10,000:1, preferably from 0.5:1 to 1000:1 and more preferably from 1:1to 20:1.

It should be understood that the preferred amount of a copper materialto be mixed with hydrazone in a given application may be influenced byavailability of copper from other sources such as copper present in thesoil or irrigation water, copper present on the foliage from naturalsources, copper applied for fungal or bacterial disease control, copperapplied as a fertilizer component, copper present in the water used inpreparing fungicide solutions for application such as in sprayapplication, copper present in formulations used in preparing spraysolutions or dusts for application, or any other suitable copper source.

For fungal control the hydrazone may be applied before or after theapplication of copper such that the mixture is generated in the locationwhere fungal control is desired. Additionally, multiple applications ofcopper or the hydrazone may be applied.

As a seed protectant, the amount of toxicant coated on the seed isusually at a dosage rate of about 10 to about 250 grams (g) andpreferably from about 20 to about 60 g per 50 kilograms of seed. As asoil fungicide, the chemical can be incorporated in the soil or appliedto the surface usually at a rate of 0.5 to about 20 kg and preferablyabout 1 to about 5 kg per hectare.

The compounds of the present invention may have broad spectrumfungitoxic activity, particularly against phytopathogenic fungi. Theyare active against fungi of a number of classes including Deuteromycetes(Fungi Imperfecti), Basidiomycetes, Oomycetes and Ascomycetes. Moreparticularly, the method of this invention provides for activity againstorganisms including, but not limited to, Phytophthora species,Plasmopara viticola, Pseudoperonospora cubensis, Pythium species,Pyricularia oryzae, Colletotrichum species, Helminthosporium species,Alternaria species, Septoria nodorum, Septoria tritici, Leptosphaerianodorum, Ustilago maydis, Erysiphe graminis, Puccinia species,Sclerotinia species, Sphaerotheca fuliginea, Cercospora species,Rhizoctonia species, Uncinula necator and Podosphaera leucotricha.

Any range or desired value given herein may be extended or alteredwithout losing the effects sought, as is apparent to the skilled personfor an understanding of the teachings herein.

The compounds of Formula I may be made using well-known chemicalprocedures. Intermediates not specifically mentioned in this disclosureare either commercially available, may be made by routes disclosed inthe chemical literature, or may be readily synthesized from commercialstarting materials utilizing standard procedures. Methods forpreparation of 2-hydroxyphenylketone benzoylhydrazones from2-hydroxyphenyl ketones and a benzoic hydrazide are well known in theliterature. In addition the preparation of metal complexes of thesematerials is also well known (see for example Journal of InorganicBiochemistry 1999, 77, 125-133 and Inorganica Chimica Acta 2007, 360,1753-1761, which are expressly incorporated by reference herein).Methods of preparation of precursor hydrazides are also well known.Hydrazides can be prepared, for example, from carboxylic acids such asin Maxwell et al., J. Med. Chem. 1984, 27, 1565-1570, and fromcarboxylic esters such as in Dydio et al., J. Org. Chem. 2009, 74,1525-1530, both of which are expressly incorporated by reference herein.Thus, the synthesis of any benzoylhydrazone of the present invention andits metal complex(es) is fully described where the starting ketone, andthe starting benzoic hydrazide, acid, or ester are described. Thehydrazones disclosed may also be in the form of pesticidally acceptablesalts and hydrates. Example 1 below provides a typical method for thepreparation of such benzoylhydrazones. Example 4 below provides ageneral method for the preparation of their metal complexes.

The following examples are presented to illustrate the various aspectsof the compounds of the present disclosure and should not be construedas limitations to the claims.

Example 1 Preparation of 4-trifluoromethyl-benzoic acid [1-(3,5dichloro-2-hydroxyphenyl)-ethylidine]-hydrazide

3′,5′-Dichloro-2′-hydroxyacetophenone (100 mg, 0.49 mmol) and4-(trifluoromethyl)benzhydrazide (94 mg, 0.46 mmol) were shaken togetherand heated to 60° C. in a solution consisting of 10% acetic acid and 90%EtOH (3 mL) for 24 hours (h). After cooling to room temperature, water(˜0.5 mL) was added and the resulting solid was filtered, washed withwater and ethyl ether and dried in a vacuum oven at 50° C. for severalhours to give the desired product (156 mg, 87%) as a pale yellow solid:mp 237-238° C.; ¹H NMR (400 MHz, DMSO) δ 14.37 (s, 1H), 11.80 (s, 1H),8.15 (d, J=8.1 Hz, 2H), 7.94 (d, J=8.3 Hz, 2H), 7.70 (d, J=2.4 Hz, 1H),7.66 (d, J=2.3 Hz, 1H), 2.54 (s, 3H); ESIMS m/z 389 ([M-H]⁻).

TABLE 1 Compound mp ESIMS ESIMS ¹H NMR (400 MHz, DMSO-d₆ unlessotherwise Number Structure (° C.) (+) (−) stated), δ  1

220-222 403 401 14.32 (s, 1H), 11.91 (s, 1H), 7.76 (dd, J = 7.8, 1.1 Hz,1H), 7.67 (d, J = 2.5 Hz, 1H), 7.65 (d, J = 2.4 Hz, 1H), 7.61 (dd, J =7.4, 1.8 Hz, 1H), 7.55-7.45 (m, 2H), 2.45 (s, 3H)  2

245-246 357 355 14.38 (s, 1H), 11.68 (s, 1H), 8.02 (s, 1H), 7.91 (d, J =7.7 Hz, 1H), 7.72 (d, J = 9.1 Hz, 1H), 7.70 (d, J = 2.5 Hz, 1H), 7.65(d, J = 2.4 Hz, 1H), 7.60 (t, J = 7.9 Hz, 1H), 2.53 (s, 3H)  3

260-262 355 14.41 (s, 1H), 11.65 (s, 1H), 7.99 (d, J = 8.5 Hz, 2H), 7.68(d, J = 2.5 Hz, 1H), 7.66-7.60 (m, 3H), 2.68-2.32 (m, 3H)  4

226-230 337 14.50 (s, 1H), 11.70 (s, 1H), 7.65 (dd, J = 11.7, 2.4 Hz,2H), 7.53 (d, J = 7.5 Hz, 1H), 7.45 (t, J = 7.0 Hz, 1H), 7.39-7.29 (m,2H), 2.45 (s, 3H), 2.41 (s, 3H).  5

247-253 403 401 14.38 (s, 1H), 11.68 (s, 1H), 8.14 (s, 1H), 7.95 (d, J =7.9 Hz, 1H), 7.87-7.83 (m, 1H), 7.70 (d, J = 2.5 Hz, 1H), 7.65 (d, J =2.4 Hz, 1H), 7.53 (t, J = 7.9 Hz, 1H), 2.53 (s, 3H)  6

307-310 353 14.33 (s, 1H), 11.41 (s, 1H), 7.82-7.78 (m, 1H), 7.70 (d, J= 2.5 Hz, 1H), 7.64 (d, J = 2.4 Hz, 1H), 7.62-7.56 (m, 1H), 7.25 (d, J =8.2 Hz, 1H), 7.13 (t, J = 7.7 Hz, 1H), 3.96 (s, 3H), 2.45 (s, 3H)  7

250-253 368 366 14.25 (s, 1H), 11.98 (s, 1H), 8.26-8.20 (m, 1H), 7.94-7.88 (m, 1H), 7.85-7.78 (m, 2H), 7.67 (q, J = 2.5 Hz, 2H), 2.42 (s, 3H) 8

221-223 337 335 14.48 (s, 1H), 11.54 (s, 1H), 7.79-7.72 (m, 2H), 7.68(d, J = 2.5 Hz, 1H), 7.64 (d, J = 2.4 Hz, 1H), 7.47-7.42 (m, 2H), 2.52(s, 3H), 2.41 (s, 3H)  9

226-227 353 351 14.53 (s, 1H), 11.43 (s, 1H), 7.96 (d, J = 8.8 Hz, 2H),7.68 (d, J = 2.5 Hz, 1H), 7.63 (d, J = 2.5 Hz, 1H), 7.09 (d, J = 8.8 Hz,2H), 3.85 (s, 3H), 2.52 (s, 3H) 10

237-238 389 14.37 (s, 1H), 11.80 (s, 1H), 8.15 (d, J = 8.1 Hz, 2H), 7.94(d, J = 8.3 Hz, 2H), 7.70 (d, J = 2.4 Hz, 1H), 7.66 (d, J = 2.3 Hz, 1H),2.54 (s, 3H) 11

310-312 369 367 14.32 (s, 1H), 11.99 (s, 1H), 11.54 (s, 1H), 7.96 (d, J= 8.9 Hz, 1H), 7.70 (d, J = 2.5 Hz, 1H), 7.63 (d, J = 2.5 Hz, 1H), 6.62(dd, J = 8.9, 2.4 Hz, 1H), 6.55 (d, J = 2.4 Hz, 1H), 3.80 (s, 3H), 2.45(s, 3H) 12

327-331 367 14.28 (s, 1H), 11.76 (s, 1H), 11.39 (s, 1H), 7.71 (d, J =2.5 Hz, 1H), 7.65 (d, J = 2.4 Hz, 1H), 7.48 (d, J = 3.2 Hz, 1H), 7.10(dd, J = 8.9, 3.2 Hz, 1H), 7.00 (d, J = 8.9 Hz, 1H), 3.76 (s, 3H), 2.45(s, 3H) 13

245 352 14.55, 11.80, 11.69, 11.46, 9.82, 9.72 (6s, 3H), 7.64- 7.50 (m,2H), 7.16 (t, J = 7.9 Hz, 1H), 6.77-6.71 (m, 2H), 2.40, 2.38 (2s, 3H),2.22, 2.14 (2s, 3H); Note: rotational isomers 14

260-262 373 371 14.28 (s, 1H), 11.96 (s, 2H), 7.93-7.88 (m, 1H), 7.72(d, J = 2.4 Hz, 1H), 7.70-7.64 (m, 2H), 7.02 (t, J = 7.9 Hz, 1H), 2.52(s, 3H) 15

258-259 369 367 14.46 (s, 1H), 11.58 (s, 2H), 7.69 (d, J = 2.5 Hz, 1H),7.63 (d, J = 2.4 Hz, 1H), 7.53 (dd, J = 8.0, 1.2 Hz, 1H), 7.21 (d, J =7.0 Hz, 1H), 6.95 (t, J = 8.0 Hz, 1H), 3.86 (s, 3H), 2.45 (s, 3H) 16

314-317 375 373 14.26 (s, 1H), 12.18 (s, 1H), 11.66 (s, 1H), 7.95 (d, J= 9.0 Hz, 1H), 7.71 (d, J = 2.5 Hz, 1H), 7.65 (d, J = 2.4 Hz, 1H),7.10-7.04 (m, 2H), 2.45 (s, 3H) 17

322-325 374 14.28 (s, 1H), 12.07-11.66 (m, 2H), 7.90 (d, J = 2.8 Hz,1H), 7.71 (d, J = 2.5 Hz, 1H), 7.65 (d, J = 2.4 Hz, 1H), 7.51 (dd, J =8.8, 2.8 Hz, 1H), 7.06 (d, J = 8.8 Hz, 1H), 2.46 (s, 3H) 18

320-323 353 14.31 (s, 1H), 11.69 (s, 2H), 7.89 (d, J = 7.8 Hz, 1H), 7.71(d, J = 2.5 Hz, 1H), 7.64 (d, J = 2.4 Hz, 1H), 6.88-6.79 (m, 2H), 2.45(s, 3H), 2.31 (s, 3H) 19

378-279 351 14.33 (s, 1H), 11.75 (s, 2H), 7.86 (d, J = 7.9 Hz, 1H), 7.72(d, J = 2.5 Hz, 1H), 7.66 (d, J = 2.4 Hz, 1H), 7.41 (d, J = 7.2 Hz, 1H),6.92 (t, J = 7.7 Hz, 1H), 2.54 (s, 3H), 2.23 (s, 3H)

As exemplified below, hydrazones of the present invention, or theirmetal complexes, in a mixture with copper or in a mixture with inorganicor organic mono- or divalent copper salts or chelates (hereinafterreferred to as “copper products”) increase the biological potency ofcopper products, enabling comparable or improved efficacy at lowercopper use rates. While not intending to be all-inclusive, copperproducts which may be mixed with the compounds of the present inventionto provide enhanced potency may include the following: copperoxychloride, copper octanoate, copper ammonium carbonate, copperarsenate, copper oxysulfate, copper formate, copper propionate, copperoxyacetate, copper citrate, copper chloride, copper diammonium chloride,copper nitrate, copper carbonate, copper phosphate, copperpyrophosphate, copper disodium EDTA, copper diammonium EDTA, copperoxalate, copper tartrate, copper gluconate, copper glycinate, copperglutamate, copper aspartate, copper adipate, copper palmitate, copperstearate, copper caprylate, copper decanoate, copper undecylenate,copper neodecanoate, copper linoleate, copper oleate, copper borate,copper methanesulfonate, copper sulfamate, copper acetate, copperhydroxide, copper oxide, copper oxychloride-sulfate, copper sulfate,basic copper sulfate, copper-oxine, copper 3-phenylsalicylate, copperchloride hydroxide, copper dimethyldithiocarbamate, ammonium coppersulfate, copper magnesium sulfate, copper naphthenate, copperethanolamine, chromated copper arsenate, ammoniacal copper arsenate,ammoniacal copper zinc arsenate, ammoniacal copper borate, Bordeauxmixture, copper zinc chromate, cufraneb, cupric hydrazinium sulfate,cuprobam, nano-copper materials, and copper didecyldimethylammoniumchloride and where appropriate the hydrates of such compounds.

Salicylaldehyde benzoylhydrazones are known in the literature aschelators of metal cations (Inorganica Chimica Acta 1982, 67, L25-L27,which is expressly incorporated by reference herein), including copper.Antimicrobial activity has been reported foro-hydroxybenzaldehyde-N-salicyloylhydrazone and its copper, nickel andcobalt complexes towards Staphylococcus aureus, Escherichia coli,Aspergillus niger and A. flavus (Proceedings of the National Academy ofSciences, India 1991, Section A Part IV, Vol. LXI, pp. 447-452, which isexpressly incorporated by reference herein). However, data in thisreport showed that the copper complex ofo-hydroxybenzaldehyde-N-salicyloylhydrazone had a similar level ofantimicrobial activity to that ofo-hydroxybenzaldehyde-N-salicyloylhydrazone alone and the nickel andcobalt complexes, and provided no indication that salicylaldehydebenzoylhydrazones might show any synergistic antimicrobial effect incombination with copper.

Example 2 Effect of Copper on Fungitoxicity of Hydrazones TowardsLeptosphaeria nodorum

In vitro fungitoxicity assays against Leptosphaeria nodorum (LEPTNO)were conducted using the liquid growth medium described by Coursen andSisler (American Journal of Botany 1960, 47, 541-549) except that coppermicronutrient, normally included as CuSO₄, was omitted. The medium,termed “copper-minus”, was prepared by dissolving 10 g glucose, 1.5 gK₂HPO₄, 2 g KH₂PO₄ and 1 g (NH₄)₂SO₄ in 1 liter of deionized water andtreating the solution with 0.5 g Chelex 100 resin (Bio-Rad Analyticalgrade, 50-100 mesh, sodium form, cat#142-2822) by stirring at roomtemperature for 1 h. MgSO₄.7H₂O (0.5 g) was added, and stirring wascontinued for a further hour. Trace elements (minus CuSO₄), and vitaminsdescribed by Coursen and Sisler were added from concentrated stocksolutions and the entire medium was sterilized by filtration. Mediumcontaining copper was prepared by adding CuCl₂.2H₂O to the copper-minusmedium at 20 μM. Test compounds were dissolved in dimethylsulfoxide(DMSO) then dilutions in copper-minus and copper-plus growth media wereprepared as 100 μL aliquots in flat-bottomed 96-well microtiter plates.

LEPTNO was grown on potato dextrose agar in 9 cm diameter petri dishesfor 7 days. Sterile deionized water (20 mL) was added to a culture plateand spores suspended by scraping the surface gently with a sterileplastic loop. The resulting suspension was filtered through a doublelayer of sterile cheesecloth. Filtered spore suspension (5 mL) wascentrifuged in a bench centrifuge at 2000 rpm for 2 min. The resultingspore pellet was resuspended in 10 mL sterile deionized water (which hadbeen treated with Chelex 100 resin using 0.5 g resin per liter of waterby stirring at room temperature for 1 h), and recentrifuged. The sporeswere resuspended in copper-minus medium, and the suspension adjusted to2×10⁵ spores per mL Microtiter plates were inoculated with 100 μL ofthis spore suspension and the plates incubated at 25° C. for 72 h beforeassessing fungal growth by measuring light scattering in a NepheloStarplate reader. Growth inhibition was determined by comparing growth inthe presence of test compound with growth in control wells lacking testcompound.

Results for growth inhibition by test compounds in copper-plus medium(“% Inhn Plus Copper Observed”) were compared with predicted values (“%Inhn Plus Copper Predicted”) that were calculated using the formula setforth by S. R. Colby in Weeds 1967, 15, 20-22 based on results obtainedfor the same compounds in copper-minus medium (“% Inhn Minus CopperObserved”) and the inhibition attributed to copper chloride alone, asdetermined by comparing growth in copper-minus and copper-plus mediawithout any test compound across experiments. Data are presented inTable 2. Results illustrate that hydrazones and copper produce asynergistic fungitoxic effect towards LEPTNO.

Example 3 Efficacy of Hydrazones in Mixture with Copper Against TomatoBlight (Phytophthora infestans)

Hydrazone compounds at 50 ppm in combination with 50 μM CuCl₂.2H₂O wereevaluated as prophylactic treatments applied 24 h before inoculation.Efficacy was determined based on percentage of disease control againsttomato late blight (TLB), causal agent Phytophthora infestans.Treatments were arranged in a completely randomized design with 3repetitions each. A pot with one tomato plant was considered as anexperimental unit. Hydrazones were dissolved in acetone and re-suspendedin water containing 0.01% Triton® X-100, 0.1% Atlox 4913 and 50 μMCuCl₂.2H₂O to a final concentration of 10% acetone. All treatments wereapplied to run off 24 h before inoculation using a spin-table sprayer.Inoculation with an aqueous suspension of P. infestans sporangia wasperformed using a Delta painting sprayer. Percentage of disease controlwas determined 7 days after inoculation. Data are presented in Table 2,and illustrate the efficacy of hydrazones in mixture with copper forcontrol of tomato late blight.

TABLE 2 LEPTNO LEPTNO LEPTNO % Inhn. % Inhn. % Inhn. Minus Plus PlusCompound Concn. Copper Copper Copper TLB % Number (μg/mL) ObservedObserved Predicted Control 1 0.05 0.0 97.3 7.1 89.5 2 0.05 0.2 98.6 7.396.0 3 0.05 9.7 98.6 16.2 95.0 4 0.05 4.5 98.5 11.3 74.0 5 0.05 4.0 98.110.8 91.0 6 0.05 1.5 96.2 8.5 52.0 7 0.05 1.1 98.2 8.1 79.0 8 0.05 1.797.7 8.7 90.0 9 0.05 1.0 97.8 8.1 95.0 10 0.05 4.0 98.0 10.8 93.0 110.05 6.2 83.4 12.8 93.0 12 0.05 0.7 94.7 7.7 65.0 13 0.05 0.0 97.5 7.197.0 14 0.05 10.3 97.8 16.7 76.0 15 0.05 12.6 93.2 18.8 88.0 16 0.0515.8 97.8 21.8 85.0 17 0.05 31.5 97.0 36.4 55.0 18 0.05 25.0 97.5 30.375.0 19 0.05 12.2 97.4 18.4 98.0 CuCl₂ 10 μM 7.1 ± 6.0

Example 4 Comparative Efficacy of Isolated Copper-Hydrazone Complexesand Parent Hydrazones Towards Leptosphaeria nodorum

Hydrazones and their isolated copper complexes were compared withrespect to their in vitro fungitoxicity towards LEPTNO. Copper complexesof hydrazones were prepared by precipitation from ethanol withCuCl₂.2H₂O, at a 1:1 molar ratio, as described in general by Ainscough,Brodie, Dobbs, Ranford, and Waters (Inorganica Chimica Acta 1998, 267,27-38, which is expressly incorporated by reference herein).

A general synthesis of 1:1 metal-hydrazone complexes is as follows. Thestarting 2-hydroxyphenylketone benzoylhydrazone is dissolved (orsuspended) in EtOH (generally 0.1 mmol hydrazone per mL solvent) andagitated at a temperature ranging from room temperature to 80° C. for 30min. To this solution (or suspension) is added 1 equivalent of the metalsalt (generally as a 1 M solution in EtOH). The mixture is agitated fora period ranging from 1 to 24 h at a temperature ranging from roomtemperature to 80° C. The metal-hydrazone complex generally precipitatesduring the reaction or upon cooling and is isolated by filtration,washed with EtOH and finally washed with Et₂O. In the instances wherethe complex does not precipitate, the solvent is removed and theresulting solid metal-hydrazone complex is washed with Et₂O. Propertiesof particular copper complexes of hydrazones are provided in Table 3below.

TABLE 3 Com- Com- Ratio plex pound Hydrazone:Metal mp Number NumberMetal Salt Salt Description (° C.) 20 2 CuCl₂•2H₂O 1:1 olive green245-248 solid 21 3 CuCl₂•2H₂O 1:1 olive green 242-247 solid 22 4CuCl₂•2H₂O 1:1 olive green 207-211 solid 23 8 CuCl₂•2H₂O 1:1 olive green242-246 solid

In vitro fungitoxicity assays were conducted using the copper-minusmedium described in Example 2. Test compounds were dissolved indimethylsulfoxide (DMSO) then dilutions in copper-minus medium wereprepared as 100 μL aliquots in flat-bottomed 96-well microtiter plates.Microtiter plates were inoculated with 100 μL of spore suspension at aconcentration of 2×10⁵ spores per mL, prepared as in Example 2. Theplates were incubated at 25° C. for 72 h before assessing fungal growthby measuring light scattering in a NepheloStar plate reader. Growthinhibition was determined by comparing growth in the presence of testcompound with growth in control wells lacking test compound.

Results for growth inhibition by hydrazones and corresponding isolatedcopper complexes (each at 0.1 μg/mL) are shown in Table 4. The resultsillustrate that isolated copper complexes of hydrazones are much morefungitoxic than the corresponding hydrazones.

TABLE 4 Complex Compound Hydrazone Complex Number Number Metal SaltRatio* % Inhibition % Inhibition 20 2 CuCl₂•2H₂O 1:1 20.6 96.0 21 3CuCl₂•2H₂O 1:1 34.7 98.3 22 4 CuCl₂•2H₂O 1:1 27.2 97.7 23 8 CuCl₂•2H₂O1:1 16.2 97.5 *Molar ratio of hydrazone:metal used to prepare complexes.

1. A compound of Formula 1

wherein R1 is CH3 or CH2CH3; Y2 is H, halogen, hydroxyl, nitro, cyano, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 fluoroalkyl, or C1-C4 fluoroalkoxy, Y3, Y4, Y5, and Y6 are independently selected from the group consisting of halogen, nitro, cyano, C1-C4 alkyl, C1-C4 alkoxy, C1-C4 fluoroalkyl, and C1-C4 fluoroalkoxy; with the proviso that Y2, Y3, Y4, Y5, and Y6 are not all H; if Y3, Y4, Y5, and Y6 are all H, Y2 is not hydroxyl, Cl, or F; if Y2, Y3, Y5, and Y6 are all H and R1 is CH3, Y4 is not CH3, OCH2CH3, or t-butyl; if Y2, Y3, Y5, and Y6 are all H, Y4 is not F or Br; if Y2, Y5, and Y6 are H, Y3 and Y4 are not both OCH3; if R is CH3 and Y2, Y4, and Y6 are H, Y3 and Y4 are not both OCH3 or NO2; and if R is CH2CH3 and Y2 and Y6 are H, Y3, Y4, and Y5 are not all OCH3.
 2. The compound of claim 1, wherein R1 is CH3; and Y2, Y3, Y4, Y5, and Y6 are independently selected from the group consisting of halogen, hydroxyl, nitro, cyano, C1-C4 alkyl, C1-C4 alkoxy, trifluoromethyl, CH3, trifluoromethoxy, and OCH3.
 3. The compound of claim 2, wherein Y2, Y3, Y4, Y5, and Y6 are independently selected from the group consisting of hydroxyl, Cl, Br, nitro, cyano, CH3, OCH3, trifluoromethyl, CH3, trifluoromethoxy, and OCH3.
 4. A synergistic mixture including a compound of claim 1 and copper.
 5. Use of the synergistic mixture of claim 4 for controlling the growth of fungal pathogens of plants.
 6. Use of the synergistic mixture of claim 4 for controlling the growth of fungal of mammals.
 7. Use of the synergistic mixture of claim 4 for controlling the growth of fungi on inert substrates selected from the group consisting essentially of wood, metal, and plastic.
 8. Use of the synergistic mixture of claim 4 for controlling the growth of fungi belonging to at least one of Ascomycete, Basidiomycete, Oomycete, and Deuteromycete classes of fungi.
 9. The mixture of synergistic claim 4, wherein the fungi is selected from the group consisting of Phytophthora species, Plasmopara viticola, Pseudoperonospora cubensis, Pythium species, Pyricularia oryzae, Colletotrichum species, Helminthosporium species, Alternaria species, Septoria nodorum, Leptosphaeria nodorum, Ustilago maydis, Erysiphe graminis, Puccinia species, Sclerotinia species, Sphaerotheca fuliginea, Cercospora species, Rhizoctonia species, Uncinula necator and Podosphaera leucotricha.
 10. The synergistic mixture of claim 4, wherein a growth inhibiting amount of a compound of Formula I in mixture with copper is provided as a mixture in which the total molar ratio of copper to the compound of claim 1 exceeds 1:1.
 11. The synergistic mixture of claim 1, wherein a growth inhibiting amount of a compound of Formula I is provided as an isolated hydrazone-copper complex in which the molar ratio of the copper to the compound of claim 1 is one of 1:1 and 1:2.
 12. The synergistic mixture of claim 1, wherein the compound of Formula I to be combined with copper is complexed with a metal.
 13. The synergistic mixture of claim 12, wherein the metal complexed with the compound of Formula I is selected from the group consisting essentially of Cu⁺, Cu²⁺, Fe²⁺, Fe³⁺, Zn²⁺, and Mn²⁺.
 14. The synergistic mixture of claim 1, wherein the copper is provided as at least one of the group consisting of copper oxychloride, copper octanoate, copper ammonium carbonate, copper arsenate, copper oxysulfate, copper formate, copper propionate, copper oxyacetate, copper citrate, copper chloride, copper diammonium chloride, copper nitrate, copper carbonate, copper phosphate, copper pyrophosphate, copper disodium EDTA, copper diammonium EDTA, copper oxalate, copper tartrate, copper gluconate, copper glycinate, copper glutamate, copper aspartate, copper adipate, copper palmitate, copper stearate, copper caprylate, copper decanoate, copper undecylenate, copper neodecanoate, copper linoleate, copper oleate, copper borate, copper methanesulfonate, copper sulfamate, copper acetate, copper hydroxide, copper oxide, copper oxychloride-sulfate, copper sulfate, basic copper sulfate, copper-oxine, copper 3-phenylsalicylate, copper chloride hydroxide, copper dimethyldithiocarbamate, ammonium copper sulfate, copper magnesium sulfate, coppernaphthenate, copper ethanolamine, chromated copper arsenate, ammoniacal copper arsenate, ammoniacal copper zinc arsenate, ammoniacal copper borate, Bordeaux mixture, copper zinc chromate, cufraneb, cupric hydrazinium sulfate, cuprobam, nano-copper materials, and copper didecyldimethylammonium chloride. 